Alpha furyl amide sulphonates



atented June 1, 1946 ALPHA FUBYL IE 'SULPHQNA'HE'JS Jack T. Thurston,Riverside, (Conn, assignor to American Cyanamid Company, New York, N.IL, a corporation of Maine No Drawing. Application @ctober 6, 194%,Serial It? 557,564

1 Claim. 3

This invention relates to certain new and useful compounds and to theirpreparation. More particularly, my invention relates to furylsubstituted organic sulphonates.

An object of this invention is to provide sulphonates which contain afuryl group as a substituent.

Another object of this invention is to provide organic sulphonatessuitable for the preparation of resins having cation active properties.

A further object of my invention is to provide processes for preparingthe aforementioned sulphonates.

The compounds which form the subject'of this invention have thefollowing general formula:

[ILiIHCHRX formula:

where X and R are the same as before, with a bisulphite or with sulphurdioxide in a suitable medium such as water or mixtures of organicsolvents and water. Compounds of the formula may be prepared bycondensing 1 mol of furfural with 1 mol of a substance containing anactive methyl group or an active methylene group, 9. g. compounds havingthe formula: Hz(3R wit 2%345) 2 (where R and X are defined in the samemanner as above) or vinylogs thereof.

The following examples in which the proportions are in parts by weight,except as otherwise indicated, are given by way of illustration and notin limitation and the furfural in pure.

EXAMPLE 1 Preparation of 2-cyano-3-potassium sulpho-3-aZpha-furylpropanoic acid amide Parts Furfurylidene cyanacetamide (1mol) 162 Potassium metabisulphite (0.5 mol) 111 Water A mixture of thesesubstances is heated until a clear solution is obtained. The solution isrefluxed for about 2 hours and then evaporated, leaving a light yellowsolid as a residue. About parts of a slightly hydrated product. isobtained.

EXAMPLE 2 Preparation of 3-sodiumsuZpho-3-alpha-fury!- propanoic acidamide Parts 2-alpha-furylacrylamide (1 mole) 137 Sodium bisulphite (1mol) 104 Water 100 These materials are heated on a steam bath in asuitable reaction flask until a clear solution is obtained. The solutionis heated for three hours, and it is evaporated to dryness. The residue,a nearly colorless solid, is washed with alcohol and dried. About 227parts of product are obtained.

'In order to obtain the sulphonates contem-. plated by my invention, itis apparent from the foregoing example that 1 mol of furfural reactswith 1 mol of a substance containing an active methyl group or an activemethylene group and the resulting compound in turn reacts with 1 mol ofa bisulphite or sulphurous acid. It may be desirable, of course, in someinstances to employ an excess of one'of the reactants in order to drivethe reaction to completion.

Other substances having an active methyl group or an active methylenegroup may be combined with furfural and converted to the sulphonate inaccordance with the, foregoing disclosure. Thus, for example, otheramides maynbesused, e. g.

amides of: chloracetic acid, bromoacetic acid,-

crotonic acid, sorbic acid, propionic acid, beta sulphopropionic acid,butyric acid, succlnic acid, malonic acid, lauric acid, phenylacetlcacid, sul- 3 phophenylacetic acid. oxalacetic acid, 3,5-dinitroo-toluicacid, and the like.

Compounds having the general formula:

may be converted to the corresponding sulphonate by treatment with abisulphite or with sulphur dioxide in a suitable medium such as water.Suitable bisulphites include sodium bisulphite, potassium bisulphite,ammonium bisulphite or any other desirable sulphite. such as calciumbisulphite. In general the alkali metal bisulphites are preferred. Thehydrogen sulphonates may be converted into the corresponding metal,ammonium or amine salts if desired. Ex

amples of amines for such salts are: methyl amine, dimethyl amine,pyridine, triethyl amine, themono-, diand tri-ethanolamines, etc.Another method of producing the sulphonates is by treatment of thefuri'urylidene compounds with a hydrogen halide followed by treatmentwith sodium sulphite or with the alkali metal sulphites. Thus, forexample, hydrogen chloride may be added to s-alpha-furyl propenoic acidamide and the resulting material treated with sodium sulphite. Stillanother type of sulphonate may be prepared by the condensation offurfural with a halogen substituted amide such as ehloracetamide,followed by treatment (1) with a hydrogen halide and then with asulphite or (2) with an equimolecular mixture of a bisulphite and asulphite. The bisulphite or sulphite may be a salt of an alkali metal,ammonia or any other desired metal or amine.

The sulphonates may be prepared from the furfurylidene compounds byreaction with bisulphite at temperatures ranging upwards from roomtemperature. In most instances, the reaction is advantageously carriedout at a temperature between about 70 C. and about 130 C. If sulphurdioxide be used, the reaction is preferably carried out under pressure,e. 8. 25-100 pounds per sq. in., and/or at relatively low temperaturessuch as about C. The time of reaction varies somewhat according to thecompatibility of the reactants. Thus, ii. a homogeneous solution of thereactants be employed, the reaction will usually be completed in fromabout /2 hour to about 2 hours. On the other hand, if the solution ofthe reactants is not homogeneous, 6-8 hours or even more may berequired. Generally, water is employed as the solvent medium for thebisulphite and the furfurylidene compound but if suflicient solubilityis not obtained other solvents may be used. Mixtures of water andwater-miscible organic solvents are especially suitable since the wateris a good solvent for the bisulphite, while the organic solvent is agood solvent for the turfurylidene compound. Examples of suitablesolvents are methanol, ethanol, propanol, isopropanol, tertiary butanol,dioxane, the lower alkyl mono-ethers of ethylene glycol and diethyleneglycol, such as the mono-ethyl ether of ethylene glycol, the mono-butylether of diethylene glycol, etc. Furthermore, inert ketones may beemployed as solvents for the reactants in the production of thesulphonates. In some instances it may be desirable to employ activeketones as intermediates in the preparation of the sulphonates. Thus,the bisulphite may add to an active ketone and this in turn reacts withthe furfurylidene compound, the former giving up the bisulphite to thelatter.

My fury] substituted sulphonic acids are especially suitable forresinincation with an aldehyde to produce resinous materials havingcation active properties. They are also useful in the preparation ofemulsifiers, wetting agents, dispersing agents and as intermediates inthe synthesis oi many other organic compounds.

This application is a. continuation-in-part of my copending applicationSerial No. 453,277, filed August 1, 1942.

Obviously many modifications and variations in the processes andcompositions described above may be made without departing from thespirit and scope of the invention as defined in the appended claim.

I claim:

An ethane having an alpha-furyl group and a sulphonate radical in the 1-position and an amide group attached thereto, in the 1- position.

JACK '1. THURSTON.

